[A MECHANISM FORTHE REACTION _ Mechanism for the Sy2 Reaction | Reaction HO + CH,cl —> CH,OH + cl Transition state Tho nogative hydroxido In the traneition Now the bond jon brings @ pair of state, a bond between the oxrven ‘electrons to the partially between oxygen ‘and carbon has positive carbon from ‘and carbon is formed and the the back side with partially formed chloride ion has respect to the leaving, ‘and the bond departed. The ‘group. The chlorine between carbon configuration of the bogine to move away and chlorine i carbon has inverted. ‘with the pair of partially broken. ‘electrons that ‘The configuration bonded ito ‘of the carbon the carbon. ‘atom begins to invert.[A MECHANISM FORTHE REACTION ~ Mechanism for the Sy1 Reaction ] CH, Gb Ss + oO — on ‘Aided by tho polar solvent, a chlorine departs with the ‘electron pair that bonded ito the carbon. CH OH + HOt + CH fa SP tis mucn cig + 3G Taneiton “aijernan ‘ ~ Slalet AGF oF ‘os Tees ins 8 a ne sonest tap This slow step produces AFoy, ‘ato anda chloride ion. Although not shown here, the tone ate solvate (and Reaction coordina= stabilized) by waterStep 2 ‘Step 3 on, stop 2 fest ae —H === cH-G—OtH rareo ‘cH, Is oH CH, H AG ‘Avrater molecule acting The products a ‘a5 a Lewis base donates —_tort-butyloxonium ion ‘an electron pair to the (or protonated = carbocation (a Lewis acid). __ tert-butyl alcohol). The shen she cette ateono. eacton coordinate carbon eight electrons. Hy 1H tN te ont ses cH C—O 6-H BE cH ‘Transition eh | I state 3 CHy H H CH, Hi ‘A.water molecule acting The products are tert-butyl a aBronsted base ‘alcohol and a hydronium is accepts a proton from jon. = — 8 the tert-butyloxonium ion. Reaction coordinateTABLE 6.5 FACTORS FAVORING Syi VERSUS Sy2 REACTIONS Factor Syl Sn2 Substrate 3° (requires formation of a relatively Methyl > 1° > 2° (requires stable carbocation) unhindered substrate) Nucleophile Weak Lewis base, neutral molecule, Strong Lewis base, rate increased by nucleophile may be the solvent high concentration of nucleophile (solvolysis) Solvent Polar protic (e.g., alcohols, water) Polar aprotic (e.g, DME, DMSO) Leaving group 1 > Br > Cl > F for both Syl and Sx2 (the weaker the base after the group departs, the better the leaving group)[a MECHANISM FORTHE REACTION _ Electrophilic Aromatic Bromination | Step 1 BB+ “Feb, = ae owe Olu W ae: Ye ale Sr—FeBr, or — ey — or + FeBre . a y ‘Arenivm ion Helpful Hint the penzene ring donates an electron pair tothe terminal bromine, forming the ‘Anooctostats patel _arenium ion and neutralizing the formal positive charge on the other bromine. as om, — CJ": is shown in Fig. 18.2. A proton is removed from the arenium jon to form bromobenzene ‘and regenerate the catalyst. Step 3of an Alkene [4 MECHANISM FOR THE REACTION | Scitcatalyzed Hydration CH. CH-H —, i Sept How ~cH, * Ths are dorains a slscon pa fs pokes torn themore sabe? caboeatisn i H CH H I fast al Step 2 + :O-H === CHy Q-H HAC ‘CH, = Son, bY H, ‘The carbocation reacts with a molecule of water to ieee Hs — Hs H Step 3 Pe + a ae aan + nbn Hs ba . & transfer of a proton to a molecule of water leads to the product.[4 MECHANISM FOR THE REACTION ~ The aldol Add Step 1 Enolate formation Enolate anion In this step the base (a hydroxide ion) removes a proton from the a carbon of one molecule of acetaldehyde to give a resonance-stabilized enolate. 5 a = AK, The enolate then acts as a nucleophile and attacks the carbonyl carbon of a second molecule of acetaldehyde, producing an alkoxide anion. Step 2. Addition of the An enolate An alkoxide anion: :0H ‘0° Step 3_ Protonation Ay + HOH = Ky + 30H of the alkoxide Stronger base The aldol product Weaker base The alkoxide anion now removes a proton from a molecule of water to form the aldol product.‘The Cannizzaro reaction takes place by nucleophilic addition of OH~ to an aldehyde to give a tetrahedral intermediate, which expels hydride ion as a leaving group and is thereby oxidized. A second aldehyde molecule accepts the hydride jon in another nucleophilic addition step and is thereby reduced. Benzalde- hyde, for instance, yields benzyl alcohol plus benzoic acid when heated with aqueous NaOH.[A MECHANISM FOR THE REACTION ~ Acid-Catalyzed Esterification The carboxylic acid accepts a proton from the strong acid catalyst. H Sot ~ Is 40H, 0H CL OH, 6-H “cH, —64 ots I : 5 by H-O: H CH, The alcohol attacks the protonated carbonyl group to give a tetrahedral intermediate. Diep. A proton is lost at ‘one oxygen atom and gained at another. CH—C—O-—CH, == C. = . € M CHe~ ~O—CH, | HO H Loss of a molecule of water ‘Transfer of a proton to ives a protonated ester. base leads to the esterReimer — Tiemann reaction Phenol, on refluxing with chloroform and sodium hydroxide (aq) at 340 K followed by acid hydrolysis yield salicyladehyde (o- hydroxy benzaldehyde) and a very small amount of p- hydroxy benzaldehyde. However, when carbon tetrachloride is used, saalicylic acid (predominating product) is formed. This reaction is called Reimer — Tiemann reactionQOH OH 340 K CHCl, +CHCl, + NaOH(aqg.) ————> A ONa 2NaOH = CHO -2NaCl HO 2- Hydroxy benzoic acid (Salicylic acid)Mechanism The eletrophile, dichloromethyle :CCl, is used genrated from chloroform by the action of a base. OH"+CHCl, <= HOH+ :CCl,—> Cr +:CCL Chloroform Dichloro carbene (Electrophilic) Reimer — Tiemann reaction involve electrophilic substitution on the highly reactive phenoxide ring.(a) C,H;OH ——> C,H,O” + Ht Phenol Phenoxide (b) Attack of electrophile (:CCI,) on phenoxide ion. Oo ° rae CCl, CC eeeCH(OH), e Om NaOH —Hyeroisis